Treatment of petroleum oils



Patented Dec. 2, 1947 BEST AVAILABLE "coPY' assists murmur or rmaonsum oms Nicholas 1. mm and John N. Datesh,

re I No Drawingi Application February "I. 1945,

4 (oi. as -sel The invention relates generally to the Treatment of petroleum oils for breaking up oil-water emulsions and more particularly to the treatment of fuel oils for separating out the water content therein and breaking up or removing the sludge which accumulates in storage tanks, heating vessels and feed lines for fuel oils: and this application is a continuation in part of our copending application Serial No. 531,988, filed April 20, 1944.

The novel compound or composition of matter, to which this invention relates,'distinguishes from other preparatlonswhich merely break up oilwater emu sions, in that our compound acts' to remove sludge. prevents its formation, and reduces the tendencyof the fuel oil to cause carbon accumulation in'the tanks. pipes and burneIrs: in addition to breaking up oil-water emul- S 0118.

Oil-water emulsions are present in fuel oil due to incomplete removal of water therefrom during refining, and to absorption of water caused by sweating in storage tanks. This emulsion is normally stable because of the presence of emulsifying agents and probably because of electrical charges carried by the water globules, so that the oil and water do not'separate by gravity 8 one.

Fuel oil contains carbon and asphaltum or tar particles which form a gummy mass commonly known as sludge, and this sludge absorbs water and causes heavy deposits on the'walls of the storage tanks, feed lineapreheaters and burners in fuel all systems.

Our novel composition contains certain organic compounds which not only aid in'breaking up the emulsions but also act as solvents for some of the asphaltum and tarry materials commonly found in fuel oils. which materials ordingrily reduce the fuel value or emciency of the S.

The stability of the oil water two phase emul sion is believed to'be attributable to the electrocolloidal activity of small clusters of mind water globules, to the high surface and interfacial tensions of the oil, and to the presence of emulsion stabilizing materials found in the oils. The problem of breaking down'these oil-water emulsions involves theselectlon of demulsiilers which contain substances capable of reducing the surface and interfacial tensions: substances which will neutralize the-electrical charges: and materials which will dissolve or counteract the emulsion stabilizing substances.

Certain prior preparations arecapable of per.

forming these functions to a substantial extent, and maybe satisfactory for treating field oil emulsions where settling, filtering or centrliug lng methods are sometimes practical, and where such methods do not'produce other disadvan- However, in the treatment of fuel oils. additional factors must be considered and additional prcblems'must be solved. The grouping of the electricallycharged oil globules causes impurities such as asphaltum, tarry and resinous particles to-be entrapped in the emulsion, contributing materially to the'formation of sludge. When demulsiflcation of such oils is brought about, some of these'foreign substances may remain in colloidal suspension, whereas others may coalesce and settle. causing sludge formation in the bottom of the tanks and feed lines. and this may subsequently result in carbon formation in preheater'lines if'a hlghenough temperature is encoimtered.

The presence of colloidaily suspended foreign substances tends to cause an increase in the viscosity of the oil. which is an objectionable conditionin fuel oil combustion, and to cause carban to accumulate at the burners.

Thus, in addition to ordinary demulsification, the conditioning'of fuel'oils'requires treatment of the oil to'dlssolve, remove or counteract the oblectlonableforeign particles entrapped in the emulsiomto reduce the viscosity of the oil, to bring about rapid demulsii'lcation preventing settling of sludge'forming particles. to remove acoumulated deposits in the tanks and lines and at the burners. and to'eliminate the necessity of centrifuging. a

In heating vessels, the deposits or formations of sludge decrease the efilciency of heat transfer and cause clogging in the feed lines and at the burners. Moreover, the increased viscosity of the oil.due to the presence of sludge requires more power'for pumping it through the feed lines to the burners.

It is therefore an object of the present invention to provide a novel composition or chemical compound for treating fuel oil which will break up-or dcmulsify the oil-water emulsions contained Another object-is to-provide a novel composition for demulsifying fuel oil which also acts to prevent-sludge formation.

- A furtherobject is to provide a novel composition for demulsifying fuel oil which also removes and prevents accumulated deposits in storage and heatingvessels, in-leedlines, and at the burners.

BEST AVAILABLE COPY assures 3 Another object is to provide a novel composition for treating fuel oil which acts to decrease its viscosity and to improve combustion.

A still further object is to provide a novel composition for treating fuel oil which simultaneously accomplishes all of the foregoing objectives.

These and"-pth',er objects arejaccompllshed byf; treating field oil with thenovel position :om--

rising the present invention. which is hereinto after set forth in detail and defined in the ap lppended claims.

The novel and improved composition-er enema cal compound which we have discovered'imesDe-icommonly made from neutral oils to which have been added coal tar acids; or (2) products obtained from the treatment of acid sludge recovered from the action of sulfuric acid on cracked petroleum distlllates, the material having boiling points in the neighborhood of 360 F. The tar acid oil can be made up of neutral oil and cresylietfacid, thefneutrai oil 'be'ingmade from petroleum products and--thcresylic acid produced in petroleum distillation.

with respect to the action of the ingredients in our novel-composition in treating petroleum oiis,'we havereason to believe that the following 'actionsor results'rtake place, although we do not cially adapted for treating fuel oils, but can also-"airm n t b it by these theories.

be used in treating oil field oils..and preferably mately the proportions given:

Ethylene dinh'lnridn '1 We.=have found that methyhpropyl-or butyl alcohol may be; used inplace of ethyl alcoholwith equally: good' results; These alcohols are properly defined as saturated alcohols having not more than four carbon atoms.--. For treating oer-- tain types of fuel oils; pine oil maybe substituted for alcohol. i 1. i

If desired. about 1% of-psradichlorobenzene orlts-equivalent-may be added to impart a pleasing odortothe compound.

Chlorinated hydrocarbons which: are solventsfor term. resins and gums include ethylene-dichloride, and other compatible hydrocarbonaof' this group may be substituted for the ethylenedichloride. a

The novel compound in theapproximate-purportions given has: been foundto be very satis'-' factory. for example'in treatin a-typicalNo. 6-

fuel oil, known as Bunker-Coil. v

It is to-bezunderstood that the proportions of the ingredients-can be variedvto'some-extentr and still-come withinthe scope of the-invention. n p act cecslisht variationstofthe Pr portionsmay'be desirable; :because of different character-- istics-of various types offuel'oii being treated.

In preparing the novel composition, the phenol,. alcohol and ammonium linoleate-are preferably l j The tar-acid ;oil -is more effective in breaking consists of t e following in i nt in pp i ltfij unemulsionsthan are water soluble colloids, be-

"the acids in thetar oil are more readily conveyed to the oil-water interface and hence go attack the film of the emulsifying agent more Cresylic :acidJsap-mixture. of three forms of cresol and contains phenol and higher-phenols.

The action of the cresylic acid is due to the forgg mation'of salts of cresol and phenol components and to theformation of fatty acids,' both of which result from: the reaction of -the=-cresols and phenols, which are contained in the cresylic acid, with the nmmonium-linoleate: The salts of the so phenol and cresol components are soluble in mineral oils. iand the-fatty;- acids attack. the-emulsion films Cresylic'acia,v is believed torbe more effective than phenol in this respect.-:

Benzolf-andphenolare effective as active ingredients attacking. the sludge formed as a resuit'of-thecarbon and asphaltum materials in the oil,- arei-also: useful: in: removing the carbon deposits; and'in dissolving asphaltum materials and certain resins.

4o Phenol-alsor acts-.: asa-: demulsifler due to the formation of phenoiates'. and: fatty acids resulting from: thereaction of'phenolf with ammonium linoleatex. -The;'products of" the: reaction attack the emulsion film.-

Referring to ammonium-llinoleate. which is the ammonium'saltiof iinoleic acid, this ingredient may beadded'as such-to the comp'osition, or may be formed by adding concentrated ammonia (26% 'to.50%-NH.1)- and'linoleicacid;

- -We believeflthat' the'presence'of ammonium lin'oleate in: our novel composition increases the soiubilitiof oresyllc 'acid'in' water, provides a,

fatty 'acid for: attaching the" emulsion film, and provides a monovalentcation which may functhoroughly mixed together inithe givenrproporiso tion to-reduceth'e' stabiliaing'eflect of the elections and heated to about 150 to 180 1. and tri'cal'charg'e presentin oil-water emulsions. then allowed to cool: The other ingredients are Theralcohols previously referred' to are solthen added and-thoroughly intermixed;- ventsforthe impurities in the fuel oil, and aid However, we do not intend to'limit ourselves infdemulsiiication' and in controlling the viscosto the exact order and' manner of mixing the in-' 00' ity ofthefuel'oil; sredients, as good results in treating fuel oil or Ethylene dichloride and other compatible chlotars used as fuel oil are not'primarily dependentriiiated'hydrocarbons, are'solve'nts for as haltum. 119011 a particular manner of preparingrthe novel? tan-y or certain resinous impurities found in fuel mposition. i oil, which' 'impurities cause sludge and carbon While all of the ingredients listedz are desir-' us formations in oilst'orage tanks, heating vessels able and preferable for obtaining best results and'fee'd'lincs, and cause carbon formation at the in treating fueloil, we consider that phenol," burners; thus' reducing'combustion'efliciency. cresylic acid, house]. ethylene dichloride or'othei" -In' the"treatment of fuel oil the amount of compatible chlorinated hydrocarbon, and" tar the: novelzcompositio'n used variessomewhat acacid oil are the more important ingredients for to cordingto tlie'nature and'the viscosity of the oil accomplishing the objects of the'invention.

The tar acid oil includes either"'(-l') products obtained in-coai tar distiliation coh'siating of coal tar'oils and coaltaracidatho' material havin being treatedi'but for treating-a typical No. 6 oil the following exampleis given:

- Add about one gallon of 'the'novel composition to each 1000 gallons of fuel'oii for the first treatbollml Wilts inthe" amperage of 350' 1;, "ll ment,'or until; the sludge is'brok'en up or dissolved.

BEST AVAILABLE COPY 8 sisting of about '75 parts by weight of tar acid oil, about 8 parts by weight of cresylic acid, and about 8 parts by weight of benzol.

8. A composition for demulsifying fuel oils and removing and preventing sludge formation, consisting of about 75 parts by weight of tar acid oil.

We have also discovered that heating the oil 4 to temperatures of from 50' I". to 180' 2. during eatment will aid the demulsifying action'of our novel composition.

We have found in actual practice that the use of the novel composition described herein has produced'remarkabieresults intreating fuel oil as used in industrial installations. particularly in preventing the formation of sludge and carbon deposits, as well as removing previously accumulated deposits. in storage'tanks, feedilines, preheaters and at the fuel burners, while at the same time reduclng'greatly the-water content of the fuel oil and increasing the fluidity of the oil.

Our novel composition is economical and eas- 11y and eflectively applied in treating various fuel oils in common use.

We claim: a

1. A composition for dcmulsifying petroleum oils and removing and preventing sludge formation therein, consisting of about 8 parts by weight of phenol, about 8 parts by weight of cresylie acid, about 3 parts by weight of benzol, about 75 parts by' weight of tar acid oil, about 1 part by weight of ammonium linoleate, about 3 parts by weight of alcohol, and about 7 parts by weight of ethylene dichloride.

2. A composition for demulsifying fuel oils and removing and preventing sludge formation, conabout 8 parts by weight of eresylic acid, about 3 parts by weight of benzol and about 3 parts by weight of phenol. 4. A composition for demuisifying fuel oils and removing and preventing sludge formation, consisting of about 75 parts by weight of tar acid oi], about 8 parts by weight of cresylic acid, about 3 parts by weight of benzol, and about 3 parts by weight of a saturated alcohol having not more than four carbon atoms.

- NICHOLAS J. DATESH. JOHN N. DATESH.

nmnnivcns 0mm The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,680,004 De Groote Feb. 21, 1928 1,882,444 Peirce et a1. Oct. 11, 1932 1,940,398 De Groote et a1. Dec. 19, 1933 2,353,700 De Groote et a1 July 18, 1944 2,365,853 Agruss et al. Dec. 26, 1944 OTHERREFERENCES Dunstan et al., "Colloids in Petroleum and in the Petroleum Industry." in Journal of the Society of Chemical Industry, vol. XLIV, page 439, Aug. 28, 1925. 

